Fluorinated oxidant compounds containing a fluoramino group

ABSTRACT

1. A compound of the formula:   and -NX-,   and -NX-, X is selected from the class consisting of hydrogen and alkyl groups containing not more than six carbon atoms, R is selected from the class consisting of mono-, di- and tricovalent ionic charge bearing groups, A AND B EACH HAVE VALUES FROM 1 TO 3, M AND N ARE THE IONIC CHARGES OF THE INDIVIDUAL FIRST AND SECOND IONS AND HAVE INTEGER VALUES FROM -3 TO +3, P IS THE COVALENCE OF R, r is the covalence of E and Q IS 0-1; PROVIDED THAT MA EQUALS -NB, THAT WHEN R IS 2, P IS 1 AND THAT WHEN D is NF, q is 0.   D is selected from the class consisting of -NF2, -NFH and NF, Y is selected from the class consisting of -O-, -N CH-, -O-N CH,   WHEREIN THE EXPRESSION INSIDE THE OUTER BRACKETS REPRESENTS A FIRST ION AND Z represents a second ion of opposite charge from the first ion, and A is selected from the class consisting of fluorine and difluoramino groups, E is selected from the class consisting of fluorine, difluoramino, perfluoroalkyl, difluoramino-substituted perfluoroalkyl, difluoramino-substituted perfluoroalkylfluoramino and

United States Wright et a1.

ate

1 1 Aug.7, 1973 FLUORINATED OXIDANT COMPOUNDS CONTAINING A FLUORAMINO GROUP [73] Assignee: Minnesota Mining and Manufacturing Company/[St Paul, Minn.

[221 Filed: May 29, 1963 [21] Appl. No.: 286,881

[52] US. Cl 149/109, 149/88, 260/293.89, 260/4655 R, 260/482 R, 260/482 C,

R, 206/563 R, 206/564 R, 260/566 A,

260/566 AE, 206/569, 206/583 NH, 206/584 [51} Int. Cl C06b 15/00, C07c 87/22 [58] Field of Search 260/583, 465.5, 293.89,

260/4655 R, 482 R, 482 C, 501.1, 501.14, 534 R, 551 R, 563 R, 564 R, 566 A, 566 AE, 569, 583 NH, 584 C; 149/88,109

Primary ExaminerLeland A. Sebastian Attorney-Frank A. Steldt, Donald C. Gipple and Temple Clayton EXEMPLARY CLAIM 1. A compound of the formula:

[ ii-hi wherein the expression inside the outer brackets represents a first ion and Z represents a second ion of opposite charge from the first ion, and.

A is selected from the class consisting of fluorine and difluoramino groups,

E is selected from the class consisting of fluorine,

difluoramino, perfluoroalkyl, difluoramino-substituted perfluoroalkyl, difluoramino-substituted perfluoroalkylfluoramino and groups, D is selected from the class consisting of NF,,

-NFH and =NF,

Y is selected from the class consisting of -O-,

N=CH, ON=CH,

and NX-,

X is selected from the class consisting of hydrogen and alkyl groups containing not more than six carbon atoms,

R is selected from the class consisting of mono-, diand tricovalent ionic charge bearing groups,

a and h each have values from 1 to 3,

m and n are the ionic charges of the individual first and second ions and have integer values from 3 to +3,

p is the covalence of R,

r is the covalence of E and provided that ma equals nb,

that when r is 2, p is l and that when D is =NF, q is O.

18 Claims, No Drawings FLUORKNATED OXHDANT COMPUUNHS CONTAINING A FLUORAMHNO GROUP This invention relates to fluorinated compounds and more particularly to certain ionic compounds containing fluorinated oxidant groups in either or both ions.

Fluorinated oxidants have been known heretofore, those of high oxidizing power being of use in propellants and explosives and those of lower oxidizing power being of use as bleaches. Previously known fluorinated oxidants of high oxidizing power have generally been relatively volatile, hydrophobic and somewhat miscible with polymeric binders commonly used in composite propellants, e.g. hydrocarbon, fluorocarbon and cellulosic binders. These properties have often been disadvantageous. In solid propellants, for example, essentially non-volatile constituents are desired for ease and safety of fabrication and storage and dependability of performance on firing. Further, any miscibility of the oxidant with the polymeric binder in a composite propellant composition often tends to weaken the grain physically and/or increase the shock sensitivity thereof. Thus, fluorinated oxidants of sufficiently high oxidizing power to be of value in such propellants have been, at best, difficult to use. Further, the volatility and hydrophobicity (i.e. water insolubility) of the fluorinated oxidants have often been disadvantageous with respect to their use as bleaches.

It is an object of the present invention to provide a novel and useful class of fluorinated oxidants which are normally solids or low-volatility liquids. it is another object of the invention to provide non-volatile solid ionic compounds containing fluorine bonded to nitrogen. It is another object of the invention to provide useful salts which contain oxidizing fluorine-nitrogen groups in either the anion or the cation or in both. it is another object of the invention to provide fluorinated oxidizing agents which have a high degree of compatibility with (i.e. can be easily used with) complementary constituents of high performance solid propellant compositions such as polymeric binders. It is another object of the invention to provide fluorinated oxidizing agents of low volatility which have very low solubilities in polymeric binders. it is another object of the invention to provide low volatility, water soluble ionic compounds useful as bleaches. Other objects of the invention will become evident from the following specification.

In accord with the above and other objects of the invention, it has been found possible to prepare stable, essentially non-volatile (i.e. having a volatility of less than 1 mm. of mercury at 25C.) ionic oxidant salts of the formula:

[.PEQ M},

wherein the expression inside the outer brackts repre sents a first ion and Z represents a second ion of opposite charge from the first ion, and

A is selected from the class consisting of fluorine and difluoramino groups,

E is selected from the class consisting of fluorine, difluoramino, perfluoroalkyl, difluoramino substituted perfluoroalkyl, difluorarnino substituted perfluoroalkylfluoramino and Q P T D is selected from the class consisting of --NF -NFH and =NF, Y is selected from the class consisting of O,

X is selected from the class consisting of hydrogen and alkyl groups containing not more than six carbon atoms,

R is selected from the class consisting of mono-, di-

and tri-covalent ionic charge-bearing groups,

a and b each have values from I to 3,

m and n are the ionic charges of individual first and second ions and have integer values from 3 to +3 (not zero),

p is the covalence of R,

r is the covalence of E and q is 0-1;

provided that ma equals -nb and provided that when r is 2, p is l and provided that when D is =NF, q is 0.

The carbon atom shown in the foregoing general formula is bonded directly to a nitrogen or oxygen atom in Y. E in that formula preferably contains not more than five carbon atoms.

A preferred class of compounds of the invention are those in which R is TV wherein T is a single covalent bond, an alkylene group containing 1 to 18 carbon atoms, an arylene group containing 6 to 12 carbon atoms or an aralkylene group containing 7 to 14 carbon atoms and V is an ionic group and includes can aslybe" The ionic nature of the salts of the invention can be conveniently demonstrated by noting the significant increase in the conductivity of acetonitrile when such salt is added thereto. in general, in the compounds of the invention the algebraic sum of the pl(,, of the conjugate base of the cation and the pl(,, of the conjugate acid of the anion is less than 13. Thus, as will be shown hereinafter, salts of the invention can be prepared by the reaction of a strong acid with a weak base and vice versa.

The ionic compounds of the invention which are particularly useful as explosives, monopropellants and solid rocket fuel ingredients are those of which 50 to 70 per cent of the total weight is made up of fluorine bonded to nitrogen and of oxygen. It is this group of compounds which have the high oxidizing power required for propellant compositions yet which have the desirable physical properties and compatibility with other propellant constituents which are required for this application.

Referring to Z in the foregoing general formula, when the compounds of the invention are to be used as explosives or propellants a preferred class of anions includes those which contain significant amounts of energetically bound oxygen or fluorine such as C10,, N C BrO I0 and anions which contain nitrogen bonded to fluorine and a preferred list of cations includes Li*, Na*, K*, Mg, Be, NHfi, NH NH and cations which contain nitrogen bonded to fluorine. Thus salts in which the ion Z falls within the definition of the first ion within the outer brackets in the foregoing general formula are also included in the invention.

A particularly preferred class of compounds of the invention for explosives and propellant uses are those in which the N-F bearing group is in the cation and the anion is perchlorate. Since the precursor perchloric acid is very strong (having a pK, of -8), it forms salts with a wide variety of bases, including very weak bases. In addition, the perchlorate anion itself contributes materially to the oxidizing power of the compound. The calculated specific impulses of several of these compounds are given in the following tables.

Monopropellants Chamber Structure lsp Temperature C. ClO H NOC(NF 232.5 2757 ClO, l-l:,N"CH,OC(NF,) 273.7 35 94 CIO{H;,N CH,CH,OC(NF,) 296.8 3935 Solid Propellants Composition Chamber (weight l,,, Temp. C. 54 ClOfH,N*OC(NF,) 16 Li 30 C,F,NO( l) 29 l .4 3975 54.3 CIO H:N*CH OC(NF,) 15.7 Li

3OC,F NO 284.7 3788 54.6 ClOfH,N*CH,CH,OC(NF,), l5.4 Li

30C,F,NO 279.8 3532 (l) C,F NO is a copolymer of tetrafluoroethylene and nitrosotrifluoromethane which is used as the binder.

Compounds of the invention can be prepared by adding a compound containing at least two reactive functions in which at least one function contains active hydrogen carried by a nitrogen or oxygen atom (sometimes referred to herein as the addend compound) across a double bond in a fluorinated oxidant compound of the formula:

wherein A and E are as previously defined. Illustrative compounds of this type are as follows:

These madameaaatsimn eoapausas can be prepared by two general routes. Those compounds which contain perfluoroalkyl groups of more than one carbon atom are prepared by reductive defluorination of the corresponding saturated difluoramino perfluoroalkyl compounds (which are prepared by methods such as those described by Lovelace et al., Aliphatic Fluorine Compounds, pages -23 (1936), Reinhold Publishing Co., New York) with suitable reducing agents such as ferrocene. Direct fluorination, as by the use of the Simons fluorination call, can also be used to prepare the starting materials for reductive defluorination. The other fluorimino compounds, all of which contain an alternating nitrogen-carbon skeletal structure, are prepared by the direct fluorination of starting materials such as ammeline, guanidine, biguanide and melamine or the hydrofluoride salts thereof. The fluorimino compounds are isolated and purified by gas-liquid chromatography in which high boiling fluorocarbon compounds are used as the stationary phase. Methods for the production of these compounds are disclosed in the co-pending applications of our co-workers, Ser. Nos. 99,632, filed Mar. 30, 1961; now U.S. Pat. No. 3,461,162,;19,111, filed Mar. 31, 1960 now U.S. Pat. No. 3,354,216,; and Ser. No. 19,112, filed Mar. 31, 1960, now abandoned.

Broadly the addend compounds which are useful in preparing the compounds of the invention include those containing hydroxyl or primary or secondary amino groups which can add to fluoramine functions and also groups which are ionic in nature such as salts of very strong acids with amines, amidines and hydrazides or groups which can be converted to ionic groups such as carboxylic acids, carboxylic esters, carboxylic amides, nitriles, sulfonic acids, sulfonic acid esters, sulfonic acid amides, oximes, hydroperoxides, tertiary amines and monosubstituted acetylenes.

The reaction in which the addend compound contains a group which is convertible into an ionic group can be represented as follows:

wherein A, E, Y, p and r are as previously defined as Q is a group which does not enter into this reaction and which is convertible into an ion bearing group (R) having m (i.e. 3, 2, 1, +1, +2 or +3) ionic charges.

When the addend compound contains an ionic group, the reaction can be represented as follows:

The NFH adduct products of either of the foregoing reactions are convertible by fluorination into the corresponding NF adducts or by elimination of HF or HNF by the action of heat or base into the unsaturated =NF compounds, e.g.:

The adducts of the type can be converted to compounds of the invention by transforming the unreacted function Q to the ion bearing group R using various methods, the method which is used for a particular addend depending largely upon the nature of the addend used in preparing it. Thus:

A. When the unreacted function is a carboxylic acid group, the intermediate adduct can be neutralized with a base to form the salt. Addends used in preparing such intermediate adducts are:

H HOGH C-OH, HOCHCOOH, noomonzcoofi HO HoooH B. When the unreacted function is a potentially acidic group, the intermediate adduct can be hydrolyzed to the acid and neutralized to obtain the salt or saponified to obtain it directly. Suitable addends include:

o o" 6 I l l Howmudom, mmormxdoa HoN=cmoHmbom o HON=CHJlORa HO(CH:1)1CEN, rrowrmxsoacmcm,

and HOCHZCHESOZNHZ, where x is 1 to 18.

C. When the unreacted function in the intermediate adduct is a potentially basic group, it can be converted to a base and the product neutralized with an acid to form the salt or it can be converted directly to a salt by hydrolysis. Where the potentially basic group is an ester, it can be converted to a hydrazide using hydrazine and where it is a nitrile, it can be converted to a hydrazidine or amidine using hydrazine and ammonia and these then treated with acids to form salts. Suitable addends include:

SIC.

0 HOCHzCHzI/ U (CHa)zC=NOH, HO(CHz)xgOR 0 O H t i H N(CHz);COR HON=C(CH;) OR, H NHOH,

and HO(CH ),C E N wherein x is as previously defined.

D. When the functions of the addend are identical 20 H H HO(CH );OH, HON=C(CH;),C=NOH, HON=CHCH=NOH, 30

and HocmomQcmomoH.

E. When the unreacted function is weakly acid, the adduct can be reacted with a strong base (e.g. LiC.,H,,) to form the salt. Suitable addends are: HO(CH ),C-CH, HOCH,CH,OH and H 0 F. In certain cases one salt of the invention can be prepared from another by metathesis, e.g. the 40 C10, salt can be prepared from the chloride salt by reaction with AgClO, in ethanol and the B ll; salt can be prepared from the chloride salt and NaB l-l, in a suitable solvent. Similarly the chloride ion in the chloride salt can be replaced by many other ions by treatment with a suitably prepared ion exchange resin.

The properties of the fluorinated oxidants must of course be taken into consideration and overheating of sensitive compounds must be avoided. Many of the compounds of the invention have a very high N-F content and may explode with high energy release. Caution must be exercised during the preparation and manipulation of these products such as performing operations behind suitable shields and wearing protective jackets, gloves and ear plugs to prevent personal injury in the event of explosions. The occasional explosion of perfluoroguanidine when frozen to l96C. during vacuum transfers is largely avoided by transferring invacuo at temperatures above the melting point of perfluoroguanidine, e.g. l l 1C., using a fluorotrichloromethane slush bath as the cooling medium.

Except for the foregoing, however, the reactions of types A.-F. above can be carried out by methods generally known to those skilled in the art.

Once the compounds of the invention have been prepared, a number of purification techniques can be used. Their high stability toward air and moisture permits the use of the conventional techniques of recrystallization, solvent extraction, ion-exchange and liquid column chromatography. The latter technique is of great value when coupled with thin layer chromatography techniques which permit the choice of proper supports and solvents using very small quantities. In some cases, sublimation is of value in the purification of these compounds.

The compounds of the invention are liquids or solids having strong oxidizing power. They are useful as explosives and for incorporation into propellants as the oxidant component and for other applications in which their oxidizing power can be utilized, as, for example, as bleaching agents and the like.

The following examples will more specifically illustrate the preparation of the compounds of the inven' tion. All parts are by weight unless otherwise specified.

EXAMPLE 1 Preparation of by the following reactions:

To a glass ampoule charged with 42 mg. of the methyl ester of glyoximic acid and 0.1 ml. of dry acetonitrile is added 57 mg. of perfluoroguanidine at l96C. The ampoule is sealed andallowed to warm gradually to 25C. At the end of 12 hr. at 25C. the solvent is removedunder vacuum and to the residue (which is nearly pure CH,OCOCH=NOC(NF,),NFl-l as shown by F n.m.r. absorptions at 22.6 due to NF and at +l37.6 (1; due to NFH) is added about one ml. of trifluoroethanol. The adduct is fluorinated by circulating through this solution, in a closed dry glass system, 0.50 mmole of fluorine in about 1500 ml. of nitrogen gas at atmospheric pressure. The fluorination is continued for 3 hr. as the temperature is raised from 23C. to 20C. The fluorinated adduct CH OCOCl-l- =NOC(NF,),, F n.m.r. 23.5 do, is thus obtained. After removal of solvent the ester moiety is hydrolyzed with 8 mg. of lithium hydroxide in about 2 ml. of 50 percent aqueous acetonitrile using moderate heating over a period of 30 min. Evaporation of the solvent yields the lithium salt which may be purified by recrystallization, solvent extraction, or other suitable means. Alternatively, the ester may be hydrolyzed by gently heating the fluorinated adduct in 2 ml. of 0.5 M hydrochloric acid for about 30 min. Neutralization of this solution with aqueous lithium hydroxide and subsequent evaporation of solvent yields the crude lithium salt.

EXAMPLE 2 Preparation of by the following reactions.

ll NHZNHC CH=NO 0mm);

lHCl

To 270 mg. of the fluorinated adduct described in Example I is added 34 mg. of 95 percent hydrazine (a solvent, such as acetonitrile may be added). The temperature of the resulting reaction is maintained below C. by cooling. At the end of one hr. the solvent, if any, is removed under vacuum and the residue, H NNHCOCH=NOC(NF is dissolved in one ml. of water containing 37 mg. of hydrogen chloride at 25C. Water is removed from the mixture after min. The resulting hydrogen chloride salt may be purified by recrystallization, solvent extraction or other suitable means.

Alternatively, the hydrochloride salt may be prepared by dissolving 300 mg. of the hydrazide described in the preceding paragraph in one ml. of the dimethyl ether of ethylene glycol. Dry hydrogen chloride gas is bubbled through this solution until precipitation of the hydrogen chloride salt is complete. The salt is filtered off and purified by the techniques described.

EXAMPLE 3 Preparation of o l oiou 'mmfiborbrvoommn,

o 0i611 IHiNHiicH=No C(NFmNFH and ll on mmnooamvoommu by the following reactions:

lHClOl ll O OlI IHaNHC-CH=NO C(NFmNFH T3270 mg. of the fluorinated adduct described in Example 1 is added 34 mg. of 95 percent hydrazine (a solvent such as dry acetonitrile may be added). The temperature of the resulting reaction is maintained below 30C. by cooling if needed. At the end of one hr. the solvent, if any, is removed under vacuum and the residue is dissolved in 1 ml. of water containing 100 mg. of perchloric acid at 25C. Water is removed from the mixture after 30 min. under vacuum. The resulting perchlorate salt of the hydrazide may be purified by recrystallization, solvent extraction or other suitable means.

An alternative method of preparation is as follows: To 203 mg. of the perchlorate salt of the hydrazide of glyoximic acid in about 1 ml. of dry acetonitrile is added 149 mg. of perfluoroguanidine at 196C. The ampoule is sealed and allowed to warm gradually to 25C. After 12 hr. at this temperature the solvent is removed under vacuum and to the residue is added about 1 ml. of trifluoroethanol. The adduct is fluorinated as described in the previous example using 0.63 mmole of fluorine in about 1500 ml. of nitrogen over a period of 3 hr. starting at 23C., warming gradually to 20C. After removal of the solvent the resulting solid may be purified by recrystallization, solvent extraction or other suitable means.

The perchlorate salt of the fluorinated adduct is also obtained by dissolving 307 mg. of the hydrochloride salt of Example 2 in 10 ml. of ethanol along with 207 mg. of silver perchlorate. The silver chloride which precipitates is filtered off. Evaporation of the ethanol yields the desired perchlorate salt of the hydrazide which may be purified by recrystallization, solvent extraction, or other suitable means.

EXAMPLE 4 Preparation of LiO'N=CH-(CH=NOC(NF,) by

. the following reactions:

sa es" F stamens gradually to 25C. After 10 days at this temperature the solvent is removed from the unreacted glyoxime and concentrated under vacuum to yield the mono-adduct contaminated with some of the di-adduct. This product is dissolved in about 1 ml. of trifluoroethanol and fluorinated using 0.50 mmole of fluorine in about 1500 ml. of nitrogen using the technique described in Example 1. After fluorination, one ml. of a solution containing 8 mg. of lithium hydroxide in water is added. Removal of the solvents under vacuum yields the lithium salt of the fluorinated adduct. lmpuritiesare removed byre crystallization, solvent extraction, or other suitable means.

EXAMPLE Preparation of by the following reactions:

' LiOH To a glass ampoule fitted with a Fischer-Porter Teflon needle valve and charged with 29 mg. of n-butyl glycolate and 0.5 ml. acetonitrile is transferred 30 mg. of perfluoroguanidine at -l10C. The valve is closed and the tube let warm to room temperature. Over a period of about 16 hrs. a high conversion to the adduct C H OCOCH OC(NF ),NFl-l is obtained as shown by fluorine nuclear magnetic resonance (F n.m.r.) and infrared analyses. The F n.m.r. absorptions are at 21.7 (doublet due to NF and 140.9 (double quintuplet due to NFH).

The adduct is fluorinated to yield C H,OCOCH,OC(NF,) (as shown by a single absorption in F n.m.r. at about 23 due to NE).

The fluorination is carried out by passing 2 percent fluorine (diluted with nitrogen) at the rate of about I00 cc/min through the adduct solution at 20C. approximately 1 hour via a stainless steel dip tube placed in the solution.

The fluorinated adduct solution is shaken with about 50 mg. of powdered NaF to remove HF which is produced as a by-product in the fluorination. The mixture is filteredby centrifuged to remove the solid.

The neutral fluorinated adduct solution is heated for 0.5 hr. (at about 60 C.) with 0.5 cc of water containing 4 mg. of lithium hydroxide. Evaporation of the solvent under vacuum yields the lithium salt Li O COCH,O C(NF which may be purified by recrystallization, solvent extraction or other suitable means.

In the glass ampoule described above is placed 16 mg. of recrystallized anhydrous glycolic acid and 0.5 ml. of dry acetonitrile. To this solution is transferred 30 mg. of perfluoroguanidine at -l 10 C.

Over a period of three days a good conversion to the adduct HOCOCH OC(N F ),NPH is obtained as shown by fluorine nuclear magnetic resonanceabsorptio ns at 21.7 due to NF and +140 (1) due to NFH.

The adduct is fluorinated as described above to yield HOCOCH OC(NF After treatment with NaF, the acetonitrile solution is mixed with 0.5 cc of water containing 4 mg. of lithium hydroxide. The product Li O COCH OC(NF is isolated as above.

EXAMPLE 6 Preparation of o l clotrtrmNnd-wmoo NFmNFH and its fluorin ation to form 0 clotmfimtii-omocm FihNFH The NaF treated fluorinated adduct solution from Example 5 containing about 60 mg. of C H OCOCH,OC(NF,) isreacted with 7 mg. of 95% hydrazine. The temperature is maintained below 30 by cooling if necessary. At the end of about 1 hour, the solvent is removed under vacuum and the crude hydrazide H,NNHCOCH OC(NF is dissolved in 0.5 cc. water containing 20 mg. of perchloric acid. Water is removed under vacuum to yield the salt CIO 'N NH -,NHCOCH,OC(NEH: which may be purifled by recrystallization, solvent extraction or other suitable means.

An alternative moethod of preparing this salt is as follows: To 95 mg. of the perchlorate salt of 2-hydroxyacethydrazide, ClO(N"H,-,NHCOCH,OH, in 1 ml. of dry acetonitrile in the apparatus of Example 5 is added mg. of perfluoroguanidine at l 10C. The valve is closed and the reactor let warm to room temperature. After about 1 week the adduct Cl0, N H NHCOCH- ,OC(NF,),NFH is obtained in moderate conversion. The solvent is removed under vacuum and to the residue is added about 1 ml; of trifluoroethanol. The adduct is fluorinated as in example 5 except that the fluorination time is increased to 3 hours. Removal of the solvent under vacuum affords the perchlorate salt ClOfN H NHCOCH O C(NF,)- which may be purifled as described above.

lid

exalt iris 7 Preparation of Li'Ci-ll t3ii 0'C(hIF by the following reactions:

l'CtHoLi niocmcmoomriii The monoadduct of ethylene glycol and and perfluoroguanidine is prepared as follows:

One tenth ml. of a dry acetonitrile solution containing 8.85 mg. (1.43 X moles) of ethylene glycol is transferred in a dry nitrogen atmosphere to a slender cylindrical dry glass vessel of 1.5 ml. capacity which is then connected to a vacuum manifold system. The acetonitrile solution is chilled to 196C. and 24.4 mg. (1.64 X 10" moles) of pure perfluoroguanidine are added by distillation, as well as a minute reference amount of tetramethyl silane. The vessel is closed and the solution allowed to warm to room temperature. After 5 days, the proton nuclear magnetic resonance spectrum shows twin weak bands centered at about -1 .21- and 0.17 and strong complex bands centered at about 5.51- and 6.21- in addition to the reference absorptions due to (CH Si and CH CN. Fluorine n.m.r. shows very weak twin absorptions at about -47 at and -4-1 5, a single sharp absorption at about -21 4 and weak doublet absorption at about 140.5 (b (estimated 1 about 50 cps). All these data are consistent with the structure: 1

To 126 mg. of HOCH CH GUNFQ NFH in a glass reactor is added 2 ml. of trit'luoroethanol. This adduct is fluorinated by recirculating nitrogen containing 6% F (a total of 1 mole equivalent F through the above solution at -20 to l0C. for a period of 7 hours.

The fluorinated adduct thus obtained has the structure HOCH CH,0C(NF as shown by a strong fluorine nuclear magnetic resonance absorption at -23.6 d due to NP, and there is absence of an absorption at +140 (,5 due to NFG.

The trifluoroethanol solution of the fluorinated ad duct is treated with Nah to remove any HF, then filtered or centrifuged to remove solid and the filtrate concentrated under vacuum. This residue is taken up in dry benzene (3 ml.) and 3 cc. of hexane containing 38 mg. of n-butyl lithium is added with stirring under anhydrous conditions at 0C. After 1 hour the lithium salt Li O'Cl-l CH OC(NF is isolated by removing the solvent under vacuum. The salt is purified by recrystallization, solvent extraction or other suitable means. it is stored protected from moisture.

EXAMPLE 8 Preparation of ClO l i l-i Cii Ci-l 0C(NF hli lhl and its fluorination of CIO N H CH OC(NF by the following reactions: 7

lid

cioniniouicmo c (NF J NFH cioiiiisgorriou o C(NFfla into a 5 ml. reactor fitted with a Fischer-Porter Teflon valve is added 0. l62 g. (l X 10 moles) of ethanolarnine perchlorate and one milliliter of acetonitrile (0.25% H 0). After degassing, 0.360 g. (2.42 X 10 moles) of perfluoroguanidine is condensed into the reactor at l 19 C. The mixture is allowed to warm to and remain at room temperature over a 2 week period. After this time, the volatile contents of the reactor are separated by fractional distillation-condensation techniques and 1.26 X 10 moles of perfluoroguanidine is recovered. The semi-solid residue in the reactor is subjected to reduced pressure for 4 hours at room temperature and then dissolved in acetonitrile. A fluorine nuclear magnetic resonance spectrum on this solution showns the major absorption at 22.0 d (NE) and a doublet at +141 .1 qb (NFH). The only other absorption is at +1491 d) and is presumed to be due to BE. These data indicate that ClO "il N Cl-l tll-i OC(NIFQ NFH is present.

To the crude reaction mixture described above which has again been dried in vacuo is added 1.6 ml. of trifluoroethanol. The resulting colorless solid suspension is then cooled to 23C. and 2 X 10 moles of fluorine (5% by volume in nitrogen) is circulated through the sample over a 6 hour period as it warms from 23 to +20C.

The colorless trifluoroethanol solvent is withdrawn from the reactor by means of a capillary syringe and placed in a nuclear magnetic resonance tube fitted with a Fischer-Porter valve. Evaporation in vacuo affords 0.103 g. of a colorless glass which is divided in half. A 0.051 g. portion of the crude product is pumped on for an additional 22 hours at room temperature to give 0.048 g. of a semi-solid which is dissolved in acetonitrile. The F n.m.r. spectrum exhibits a major band at 24.0 (15 (NE) and a less intense band at +1491 :1; (WT). Three other very minor absorptions are present at 20.6, --l9.5 and +743 qb.

The salt is purified by liquid column chromatography on a silica gel column utilizing the following order of solvents; chloroform, 50:50 chloroform-ethyl acetate, ethyl acetate and ethanol. The product, C10- N l-l CH Cll-H OC(NF which is obtained by evaporation of the ethyl acetate eluate, is a colorless solid melting with decomposition at about l88-l93C.

A sample of ClO{l l lli Ci-i ClH O(NF the preparation of which is described above is dissolved in water. The solution is slowly neutralized with 10% aqueous sodium hydroxide to a pill of 8. The precipitated yellow-colored oil is extracted from the aqueous solution with diethyl ether. The ether extract is dried with CaSO and evaporated to dryness. The free amine product, Nll-ll Ciil Cl-l OC(NF is purified by liquid column or vapor phase chromatography.

EXAMFLE 9 and H01 g l ClNHaCHrOC(NFQ)3 A sample of pure Nhydroiiyriiethylsficinimide (mp? 64.566C.) weighing 0.194 grams (1.5 X 10 moles) is placed in a dry 3 ml. ampoule fitted with a Fischer- Porter Teflon valve. Dry acetonitrile (0.8 ml. is then added to the ampoule followed by 0.373 grams (2.5 X 10* moles) of perfluoroguanidine. The reaction mixture turns an amber-color while standing for 4% days at 25C. The mixture is evaporated to dryness, subjected to reduced pressure for 25 hours (weight 0.417 grams 95% yield) and dissolved in 1.5 cc of trifluoroethanol. The F" nuclear magnetic resonance spectrum shows an absorption at 22.0 characteristic of the NF group and a doublet assigned to the NFH at +139.6 4,.

The solution of theadduct in 1.5- cc. of trifluoroethanol described above is fluorinated with 4 X 10 moles of fluorine by the procedure used in Example 8.. The fluorination is continued for a total of 16 hours at initial and final temperatures of 23 and +25C., respectively. The fluorine n.m.r. spectrum suggests an approximately 80% conversion to the tris(difluoramino) derivative by a new NF: absorption at 24.3 q) consistent with the tris(difluoramino) methyl group and disappearance of the NFH absorption at 139.6 b.

A sample of the above fluorinated adduct is dissolved in 95% ethanol which contains one molar equivalent of hydrazine hydrate. The mixture is heated at reflux temperature for a short time, cooled, filtered and the filtrate acidified with perchloric acid. The desired amineperchlorate is obtained by complete removal of the volatiles in vacuum. The salt is purified by recrystallization or liquid column chromatography.

An alternate route to HClO 'NH,Cl-l,OC(NF involves the acid hydrolysis of the aforedescribed fluorinated N-hydroxymethylsuccinimide adduct. The adduct is dissolved in a mixture of acetic and hydrochloric acids and heated to 100C. The hydrochloride salt of the desired product is recovered from the reaction mixture, dried and dissolved in ethanol. A stoichiometric amount of silver perchlorate, dissolved in ethanol,

is added to the solution and the silver chloride precipitate is filtered. Complete evaporation of the ethanol filtrate yields the desired perchlorate salt.

Another route to HCIO 'NH CH OC(NF is by heating the fluorinated N-hydroxymethylsuccinimideperfluoroguanidine adduct in aqueous perchloric acid. The perchlorate salt is recovered by complete evaporation of the solution after the succinic acid by-product is removed by filtration. Purification is accomplished by liquid column chromatography or recrystallization.

EXAMPLE 10 Preparation of HClO -NH OC(NF NFH and its fluorination to HClO 'NH OC(NF and the preparation of the latter by a different process using the following reactions:

Hydroxylamine perchlorate is prepared as follows:

Samples of anhydrous silver perchlorate (1.0 gram) and anhydrous hydroxylamine hydrochloride (0.35 gram) are each dissolved in milliliters of 100% ethanol. A potentiometric titration of the two solutions shows that l.105:t0.005 milliliters of the ethanolic hydroxylamine hydrochloride is equivalent to 1.000 milliliters of the silver perchlorate solution.

To a stirred 20.0 milliliter sample of the silver perchlorate solution is rapidly added 22.1 milliliters of the hydroxylamine hydrochloride solution. The precipitated silver chloride is removed by filtration and the clear ethanolic filtrate evaporated to dryness under vacuum. The resulting hydroxylamine perchlorate is a colorless solid melting at 8487C.

Utilizing the same general procedures as outlined previously, 0.262 g. (1.96 X 10" moles) of hydroxyl amine perchlorate and 3 cc. of dry acetonitrile are added to a dry 10 cc. ampoule (dry nitrogen atmosphere). The solution is then cooled to l l 1C., degassed to less than 0.1 mm of mercury pressure and 0.745 g. (5 X 10". moleslof perfluoroguanidine is added by condensation.

The mixture is allowed to warm to and remain at room temperature for about 7-10 days. Agitation is accomplished by means of a magnetic stirring bar which is contained in the ampoule. The solvent and excess perfluoroguanidine are removed from the reactor by vacuum transfer techniques. The F" n.m.r. spectrum of the resultant yellow, non-volatile, semi-solid residue exhibits a peak at about 33 4 assigned to the NF group and a poorly resolved doublet in the 1b region assigned to the NFH.

Fluorination of the adduct is accomplished by dissolving the material in trifluoroethanol, cooling to 23C. and circulating a dilute stream of fluorine in nitrogen through the solution as it warms to 0C. Evaporation of the fluorination solvent affords a semi-solid residue of the desired perchlorate salt. Final purification is accomplished by liquid column chromatography, recrystallization or solvent extraction.

are also formed. Alternatively the -NFH adduct may be fluorinated as a dilute solution in trifluoroethanol by bubbling dilute fluorine (about l0%) through the solution at temperatures from 50 to 25C. The desired products can be isolated by distillation or by vacuum fractionation or by gas chromatography.

A mixture of (Cl l,,) C=NOC(NF prepared as described above, and an equimolar amount of lHClO in water in a closed vessel is stirred and heated gently for thirty minutes. The water is removed in vacuo at 25C. and the desired perchlorate salt, CIO N H OC(NF is obtained as a semi-solid residue.

EXAMPLE 11 Preparation of Mg (O CCl-I NCH C(NF by the following reactions:

Mg( (2 CH a); n CHaOII ((Fzmomcnaomo 0 o m To a mixture of perfluoroguanidine in dry carbon dioxide free dimethyl ether in closed glass flask at l 1 l C. is added with stirring a cold solution of CH NHCH CN in dimethyl ether. The mixture is allowed to warm slowly to -40 C. and the dimethyl ether is removed in vacuo at -40 C.

The product'is complexed with dimethyl ether. The viscous yellow liq uid residue is fluorinated at 30C. with stirring with a mole excess of 3 percent fluorine in dry nitrogen at a flow rate of about 150 cc per minute. The yellow liq uid which remains in the flask after fluorination is mainly (F N) CN(CH )CH CN. This nitrile is gently heated with excess dilute aqueous sodium hydroxide until dissolution occurs. The solution is acidified with dilute aqueous hydrochloric acid and the acid (NF CN(CH )CH COOH, is obtained as a yellow oil. This oil is dissolved in methanol, an equivalent amount of Mg(OCH in CH OH is added, and the solution is evaporated to dryness in vacuo leaving (NF CN(CH )CH COO Mg as a solid which can be purified as described in Example 1.

lid

EXAMPLE 12 Preparation of flimomom (F N);CN=CHCH CH;i JNHOH 011 1 31136 0CH3 by the following reactions:

Perfluoroguanidine and HN==CHCH CH CN are reacted and fluorinated according to the procedure of Example ll to form (F N); C-N=CHCH CH CN. This nitrile is heated with an equimolar quantity of H NCl-l Cl-l Nl-l in ethanol and a two molar equivalent of acetic acid is added until the cooled solution is neutral. The solvent is removed in vacuo and firmomom Fmnc-N=CH0H,CH2dN1I0Inomt mrow OH;

is obtained.

EXAMPLE 13 Following the procedure of Example 5, the adduct CH OCOCH OC(NF NFH is prepared in about conversion from 63 mg. of dry methyl glycolate, mg. of perfluoroguanidine in 0.2 ml. dry acetonitrile as solvent. The F n.m.r. absorptions are at 2l.6 qB (due to NF and +140.7 (double quintuplet due to NFH).

The adduct is fluorinated to yield CH OCOCH OC(NF (single absorption in F n.m.r. at 23.4 due to NF The fluorination is carried out essentially quantitatively by continuously recirculating 3.5% F (2 equivalents, based on the reaction NFH F "+NF HF) diluted with N through a solution of the adduct in trifluoroethanol. The reaction time is 19 hours (3 hours between 23 and 20C.; 16 hours at 20C.).

The CH OCOCH OC(NF compound is purified by gas liquid chromatography at 80C. employing polydimethylsiloxane on diatomaceous earth.

The CH OCOCH OC(NF product is saponified using the procedure of Example 5 to yield Li OCOCH OC(NF EXAMPLE 14 Preparation of 1 1s cocrr coriiiicha ting the following reactions:

(ammo0omoorqmomnfiwamuei (Fmnooomoomm mmcmm rocaanioi lHlPol (mor o HrcoxoHmfiucmxsi (Fame 0 01120 0,011. nowmniucmna? "A mixture of equiniolar Ern odHs'tS t CHflCOCI-T rated to dryness with stirring in vacuo and the product,

[(F,N),COCH,CONH(CH,),N*(CH,),H130;, is obtained.

A mixture of equimolar amounts of CH,OCOCH,'OC(NF,), and HO(CH,),N (CH,),BF in acetonitrile is heated with stirring. The solvent is removed in vacuo leaving a semi-solid residue of (RN COCH,CO,(CH,) N (Cl-l,) Br.

EXAMPLE Preparation of \I N02 om ssowrm ii-Nn, 6 NO:

NF, I

An equimolar mixture of CF CF=NF and 7 +|NH1 o r'rcrownmdocnndl,

is present. Two molar equivalents of anhydrous ammonia in dry ethanol is added and after two hours the solution is decanted. The compound IIIH C FaCII W QK F m is present. An equimolar amount of picric acid is added and the solvent is removed in vacuo leaving the compound,

0 morowmndnn, 6 No,

as a yellow semi-solid.

EXAMPLE 16 Preparation of (F,N),COCH,C I C'Li by the following reactions:

HOCHgCECH (NFg)7C=NF (FgN)1COGH3CECH NFI-I CFICILOHI F,

An equimolar amount of propargyl alcohol and perfluoroguanidine is reacted and fluorinated according to the procedure of Example 7. The compound, (F,N),COCH,C I CH, thus obtained is dissolved in dry benzene and an equimolar amount of butyl lithium in heptane is slowly added. The compound, (F N COCH,C 1 CLifl is obtained as a white solid.

EXAMPLE 17 Preparation of by the following reactions:

N F ii (cmmmiorccmo NF,

The compound, HO CCH OC(NF NFH, is obtained as described in Example 5. To the acetonitrile solution containing this compound is added two molar equivalents of triethylamine with stirring at about 20C. The solvent is removed in vacuo leaving a residue which contains w]? (mmmiaoroomoolwm This compound is also obtained when a 10 mole equivalent of sodium fluoride powder is added to the solution containing H0 CCH,OC(NF )NFH and the solution is heated at 60C. for 2 hours. The solution is filtered to remove sodium fluoride and to the filtrate is added an equimolar amount of triethylamine in acetonitrile. The compound,

is obtained as a solid residue.

EXAMPLE 18 According to the procedures of Example 8, ethanolamine perchlorate is reacted with the following fluorimino compounds and the resulting adducts are fluorinated to form the products indicated.

Fluoriimted adduct salts Fluorimino compound N Fll containing adduct salts Unsaturated mldnct salts CsF7CF=NF Addend compound i C3F C O C 1120 lluNlhClO FN=C F-O CIIgClI NIhCiOi m fi (Fmigc Fxr o o ciricmNmoloi NMO FNF o 0 0 mo llzNlI Cl04 1711 2 FNF (J 0 (Jl-[zClIzNlIaGlOl AYFII (CILNIIsNCIIzCIIgOC-NFgl NF EXAMPLE 19 Preparation of the mixed salt,

vacuo at 25C. leaving the pure salt, (F N) COCH CO H N CH CH DC(N1 EXAMPLE 20 According to the procedures of' Example 19, the following salts are prepared from compounds prepared in Examples 1-19.

Reactants Ionic Product (F,N),COCH,CO,H (Ex. 5) and (F N),COCH,C0{NH NH- 2O COCH=NOC(NF,)

(F,N ),CON=CHCONHNH, (Ex.

To a mixture of 0.28 g. (1 X mole) of 2,4,6tricarbomethoxybenzyl alcohol in 0.3 ml. of acetonitrile is added 0.15 g. (1 X 10 mole) perfluoroguanidine at l 1 1 C. The mixture is allowed to react in a closed tube at C. overnight. The solvent is then removed under vacuum and 1 ml. of trifluoroethanol is added to the liquid residue. Fluorination is accomplished using the procedure of Example 1 using 2 X 10" mole of fluorine diluted to about 5 percent with nitrogen. The fluorinated adduct is converted to the sodium salt by heating the trifluoroethanol solution with about 40 mg. of sodium hydroxide dissolved in 0.3 cc. of water for minutes at 60 C. The salt is isolated by evaporation of the solvent under vacuum. Alternatively the neat fluorinated adduct may be treated with 3.4 mg. of 95 percent hydrazine (a solvent such as acetonitrile may be used). The temperature is maintained below 25 C. by cooling in an ice-bath. At the end of' 1 hour the solvent, if any, is removed under vacuum and the residue is dissolved in one ml. of water containing 100 mg. of perchloric acid at 25 C. After about 30 minutes water is removed by vacuum. The resulting perchlorate salt may be purified by recrystallization, solvent extraction or other suitable means.

EXAMPLE 22 To a solution of 0.16 g. (l X 10' mole) of the oxim e of methyl mesoxalate in 0.3 ml. of acetonitrile is added 0.15 g. (1 X 10 mole) perfluorog'uanidine at 1 10 C. The mixture is allowed to react in a closed tube at 25 C. overnight. The solvent is removed under vacuum, 1 ml. trifluoroethanol addedto the residual liquid adduct, and the adduct fluorinated following the procedure of Example 1 using 3 X 10 mole of fluorine dilut'ed to about 5 percent with nitrogen and employing a sodium fluoride scrubber to remove hydrogen fluoride from the recirculating gas stream. I

The fluorinated adduct, (F,N);,CON=C(COOCH,), is converted to the lithium salt by heating the trifluorothanol solution with 50 mg. of lithium hydroxide dissolved in 0.3 cc. of water for about 1 hr. at 60 C. The salt is isolated by evaporation of the solvent under vacuum.

EXAMPLE 23 Preparation of o II II N'ocwmnoocurm by the following reactions:

' urea nooowmncoon (FZN)IC=NF wherein the expression inside the outer brackets represents a first ion and Z represents a second ion of opposite charge from the first ion, and

A is selected from the class consisting of fluorine and difluoramino groups,

E is selected from the class consisting of fluorine, difluoramino, perfluoroalkyl, difluoraminosubstituted perfluoroalkyl, difluoraminosubstituted perfluoroalkylfluoramino and groups,

D is selected from the class consisting of NF;,

NFl-l and =NF,

Y isselected from the class consisting of O,

-N=Cl-l--, O-N=CH,

will

X is selected from the class consisting of hydrogen and alkyl groups containing not more than six carbon atoms,

R is selected from the class consisting of mono-, di-

and tri-covalent ionic charge bearing groups,

a and b each have values from 1 to 3,

m and n are the ionic charges of the individual first and second ions and have integer values from 3 to +3,

p is the covalence of R,

r is the covalence of E and q is 0-1;

provided that ma equals nb,

that when r is 2, p is l and that when D is =NF, q is 0.

2. A compound according to claim 1 wherein Z is the anion.

3. A compound according to claim 1 wherein Z is a monovalent anion.

4. A compound according to claim 1 wherein Z is a divalent anion.

5. A compound according to claim 1 wherein Z is a tri-valent anion.

6. A compound according to claim 1 wherein Z is a monovalent cation.

7. A compound according to claim 1 wherein Z is a divalent cation.

8. A compound according to claim 1 wherein Z is a trivalent cation.

9. A compound according to claim 1 wherein the expression inside the outer brackets is a monovalent anion.

10. A compound according to claim 1 wherein the expression inside the outer brackets is a divalent anion.

11. A compound according to claim 1 wherein the expression inside the outer brackets is a trivalent anion.

12. A compound according to claim 1 wherein the expression inside the outer brackets is a monovalent cation.

13. A compound according to claim 1 wherein the expression inside the outer brackets is a divalent cation.

14. A compound according to claim 1 wherein the expression inside the outer brackets is a trivalent cation.

15. A compound according to claim 1 which contains 50 to weight per cent of fluorine bonded to nitrogen and of oxygen.

16. A compound according to claim 1 wherein Z is selected from the class consisting of ClOfNOfClOf' BrO 10;, Li, Na*, K, NHJ, NH NHJ, Mg and Be.

17. A compound according to claim 1 wherein Z falls within the definition of the first ion thereof.

18. A compound according to claim 16 wherein Z is ClOf. 

1. A COMPOUND OF THE FORMULA:
 2. A compound according to claim 1 wherein Z is the anion.
 3. A compound according to claim 1 wherein Z is a mono-valent anion.
 4. A compound according to claim 1 wherein Z is a divalent anion.
 5. A compound according to claim 1 wherein Z is a tri-valent anion.
 6. A compound according to claim 1 wherein Z is a monovalent cation.
 7. A compound according to claim 1 wherein Z is a divalent cation.
 8. A compound according to claim 1 wherein Z is a trivalent cation.
 9. A compound according to claim 1 wherein the expression inside the outer brackets is a monovalent anion.
 10. A compound according to claim 1 wherein the expression inside the outer brackets is a divalent anion.
 11. A compound according to claim 1 wherein the expression inside the outer brackets is a trivalent anion.
 12. A compound according to claim 1 wherein the expression inside the outer brackets is a monovalent cation.
 13. A compound according to claim 1 wherein the expression inside the outer brackets is a divalent cation.
 14. A compound according to claim 1 wherein the expression inside the outer brackets is a trivalent cation.
 15. A compound according to claim 1 which contains 50 to 70 weight per cent of fluorine bonded to nitrogen and of oxygen.
 16. A compound according to claim 1 wherein Z is selected from the class consisting of ClO4NO3ClO3BrO3 , IO3 , Li , Na , K , NH4 , NH2NH3 , Mg and Be .
 17. A compound according to claim 1 wherein Z falls within the definition of the first ion thereof.
 18. A compound according to claim 16 wherein Z is ClO4 . 